Halogenated, diolefin-styrene polymers with terminal hydroxy groups



United States Patent 3,284,511 HALOGENATED, DlOLElFlN-STYRENE PGLYMERSWll'lH TERMINAL HYDROXY GROUPS Stanley P. Rowland, lErvin G. Pritchett,and Noel L. Hofmann, all of Cincinnati, Ohio, assignors to NationalDistillers and Chemical Corporation, New York, N.Y., a corporation ofVirginia N Drawing. Filed Dec. 13, 1961, Scr. No. 159,139 1 Claim. (Cl.260-618) The present invention relates to novel chemical compounds andto a process for their manufacture. More particularly, the presentinvention relates to polymerized derivatives of dialkali metalhydrocarbon compounds in which each of the two alkali metal atoms islinked to a different carbon atom in .an aliphatic hydrocarbon group orin an aliphatic hydrocarbon chain that may contain aromatic, e.g.,phenyl, substituents. Still more particular, the invention relates tohigh molecular Weight dialkali metal polymerized hydrocarbons and to theproduction therefrom of high molecular weight halogenated glycols.

Novel compounds embodied by the present invention are halogenatedderivatives of substantially difunctional polymers, described in detailin copending application S.N. 75,907 (filed December 15, 1960 that arevaluable as raw materials for plastics, rubbers, foams, coatings, andthe like. More specifically, they are derivatives of dialkali metalpolymeric hydrocarbons in which the polymeric hydrocarbon group has amolecular weight of at least about 300, each alkali metal atom is linkedto a different carbon atom in an aliphatic chain or inaromaticsubstituted aliphatic hydrocarbon chain, and the polymerichydrocarbon group contains more than two units of a monomer from thegroup consisting of aliphatic conjugated diolefins, styrene, andalkyl-substituted styrenes. These novel halogenated products are made byhalogenating the polymeric gly-c-ols which are prepared from polymersformed by addition of molecular units of a monomer to a relatively lowmolecular weight dialkali metal hydrocarbon until a higher molecularweight dialkali metal hydrocarbon, having a molecular weight in excessof about 300, has been built up. In a specific illustration, asufficient amount of butadiene is reacted with a mixture of isomericdisodiooctadienes (containing straight chain and branched chain isomers)to yield a disodiopolybutadiene of the desired molecular weight. Thedisodiopolybutadiene may then be reacted with, for example, an epoxidecompound, followed by hydrolysis, to yield the corresponding glycol. Theglycol is then halogenated, for example by treating with chlorine.

The process embodied herein is particularly well adapted to the use ofdilithiooctadiene, mixtures of isomeric disodiooctadienes, anddisodiodiphenylbutane as the low molecular weight dialkali metalhydrocarbon and to butadiene or styrene as the monomer to be addedthereto. The process of this invention, however, is in generalapplicable to addition products of saturated or unsaturated dialkalimetal hydrocarbons with aliphatic diolcfins, styrene, or substitutedstyrenes. For example, the starting material utilized for practice ofthis invention may be a dialkali metal dimer of an aliphatic conjugateddiolefinic hydrocarbon such as butadiene, isoprene, 1,3-pentadiene, andthe like or of an aromatic compound containing an olefinic substituentsuch as styrene or alkyl-substituted styrene, such as ot-methylstyrene,vinyl-toluene, and so forth. The low molecular weight dialkali metalhydrocarbon starting materials of this invention may, for example, be anisomeric mixture of disodiooctadienes prepared by treating butadienewith finely dispersed sodium, preferably a dispersion thereof in whichthe particle size of the sodium does not exceed about three microns, ina selected liquid medium, such as dimethy-l ether, and, if desired, inthe presence of a relatively small amount of a polycyclic aromatichydrocarbon, such as .anthracene, benzophenone, naphthalene, ortenphenyl, and/or in the presence of a selected solid, friable attritionagent at a temperature preferably below about 0 C., or it may bedisodiodiphenylbut-ane prepared similarly from styrene. Processes forpreparing such alkali metal hydrocarbons are disclosed in, for example,US. Patent Nos. 2,816,913, 2,816,914, 2,816,916, 2,816,917, and2,816,936.

In accordance with the preferred embodiment of this invention, the lowermolecular weight dialkali metal hydrocarbon is reacted with a monomersuch as, for example, butadiene, styrene, or the like. In anotherembodiment of this invention, a finely-dispersed alkali metal, such assodium or, preferably, lithium, is reacted with a monomer, such asbutadiene or styrene, to form a dialkali metal hydrocarbon, for example,by a process such as is disclosed in US. Patent No. 2,816,913. Theaddition of monomer is continued until a dialkali metal polymerichydrocarbon of the desired molecular weight has been built up. Themonomer with which the lower molecular weight dialkali metal hydrocarbonis reacted may be the same as the monomer used in making the lowermolecular weight dialkali metal hydrocarbon or different from it.

The polymerization reaction suitably is conducted in the presence of aliquid reaction medium which essentially contains certain types ofethers. The ether medium can be any aliphatic rnonoether having amethoxy group in which the ratio of the number of oxygen atoms to thenumber of carbon atoms is not less than 1:4. Examples include dimethylether, methyl ethyl ether, methyl upropyl ether, methyl isopr-opylether, and mixtures of these methyl ethers. Certain aliphatic polyethersare also satisfactory. These include the acyclic and cyclic polyetherswhich are derived by replacing all of the hydroxyl hydrogen atoms of theappropriate polyhydric alcohol with alkyl groups. Examples are theethylene glycol dialkyl ethers such as the dirnethyl, methyl ethyl,

diethy-l methyl butyl, ethyl butyl, dibutyl, and butyl lauryl ethyleneglycol ethers; trimethylene glycol dimethyl ether, glycerol trimethylether, glycerol dimethyl ethyl ether, and the like. Generally, simplemethyl monoethers such as dimethyl ether and the polyethers of ethyleneglycols such as ethylene glycol d-imethyl ether are preferred.

Although it is preferred that the reaction medium for the polymerizationreaction consist substantially of the ethers as specified, other inertliquid media can be present in limited amounts, replacing for examplefrom about 5 to about percent of the ether. Examples of these inertmedia include hexane, benzene, 'alkylate, triethylamine, and mixturesthereof.

The polymerization reaction is generally carried out at a temperaturebetween the reflux temperature of the liquid reaction medium and aboutC. or lower, and is preferably between about reflux temperature and -40C.

The amount of monomer added to the lower molecular weight dialkali metalhydrocarbon depends upon the molecular weights of the reactants and uponthe desired molecular weight of the polymerized product. In general, thedesired molecular weight of the dialkali metal polymeric hydrocarbonproduct lies between about 300 and several hundred thousand, preferably500 to 5,000 for many applications. Thus, regarding the relative amountsof reactants to employ, and in the case of reacting the alkali metalwith the monomer, use is made of an excess of the monomer over mole t-omole ratio with the alkali metal. That is, the total amount of monomerthat is employed until completion of the reaction is in excess of onemole of the monomer per mole of alkali metal, the excess of monomeremployed being, as aforesaid, dependent on its molecular weight and thedesired molecular weight of the desired polymerized product.

The polymers of this invention contain sufllcient units of the selectedmonomer to give a product having the desired molecular weight, that is,the molecular weight which will make the polymer most suitable for thedesired ultimate use. To illustrate, a polymer intended to be used forrigid or semi rigid foams will preferably have a molecular weight in therange of about 300 to 800. Polymers intended for use as flexible foamswill suitably have molecular weights in the range of about 1,000 to4,000. The molecular weight range for difunctional polymers to be usedin coatings or in elastomers for casting resins is suitably about 1,000up to about 10,000 or up to about several hundred thousand for millablerubbers.

In preferred practice of this invention, the lower molecular weightdialkali metal dimerized hydrocarbon is formed prior to the addition ofthe monomer for polymerization. It is possible, however, in anotherembodiment of this process to form the lower molecular weight dialkalimetal dimerized hydrocarbon during the addition of the monomer; that is,to start with a monomer and an alkali metal and to continue feeding themonomer into the system until the desired dialkali metal polymerichydrocarbon is formed, without stopping the reaction at the dialkalimetal hydrocarbon dimer stage. The present process may be carried outeither in a continuous, semi-continuous, or batchwise manner, and it isnot intended to limit the process to any particular method of operation.

The higher molecular weight dialkali metal polymeric hydrocarbons ofthis invention can be converted into glycols by reacting a suitablecompound with such a higher molecular Weight dialkali metal polymerichydrocarbon. Such a suitable glycol-forming reactant may be an epoxide,for example, an aliphatic epoxide such as ethylene oxide, propyleneoxide, or the butylene oxides or it may be an aromatic epoxide such asstyrene oxide. The glycol-forming reactant may also be a suitablecarbonyl-type compound, such as, for example, aldehydes; examplesthereof include formaldehyde, paraformaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, isobutryaldehyde, and the octylaldehydessuch as 2-ethylhexaldehyde. Aromatic and heterocyclic aldehydes such asbenzaldehyde and furfural may also be used, as may such aldehydes assalicyaldehyde, anisaldehyde, cinnamaldehyde, piperonal, vanillin,acrolein, and crotonaldehyde. Carbonyl compounds of the ketone classalso may be employed, for example, acetone, methyl ethyl ketone, diethylketone, .acetophenone, benzophenone, methyl vinyl ketone, metisyl oxide,phorone, and benzoquinone. It is also possible to produce glycols fromthe higher molecular weight dialkali metal polymeric hydrocarbons ofthis invention by oxidizing them with oxygen itself, either as pureoxygen or admixed with inert materials such as in dry air. Ozone alsomay be employed as well as oxidizing materials which yield oxygen or itsoxidizing equivalents. These include sodium peroxide, hydrogen peroxide,the persulfates, and other organic and inorganic peroxides, metalperoxides, nitrogen oxides, nitro-aromatic compounds such asnitrobenzene, and some met-a1 salts.

At least two equivalents of the glycol-forming reactant are required foreach molecule of the dialkali metal polymeric hydrocarbon. In order toinsure complete reaction for glycol formation, an excess of theglycolforming reactant is usually employed; for example, when using anepoxide the excess may be up to about 400 4 percent, and is preferablyfrom about 10 percent to about 50 percent.

The reaction with the glycol-forming compound, for example as in thecase of using an epoxide, is followed by treating the dialkali metalsalts of the resulting corresponding glycols with a hydrolyzing agent,e.g., water, an alcohol such as methanol or ethanol, etc., to destroyany unreacted alkali metal and to liberate the glycols from theirdialkali metal derivatives which are initially formed. The glycols areisolated from this reaction mixture by extraction, distillation, orother suitable means. The resulting glycols have molecular weightsranging from about 300 up to several hundred thousand, depending uponthe operating conditions.

The glycol-forming reaction may, if desired, take place in the presenceof a liquid reaction medium, such as an ether. When an ether is used, itis preferably selected from the aforelisted group of ethers suitable asreaction media for the addition of polymerization step. The specificether used in the condensation step is, however, not necessarily thesame ether as that employed in the formation of the higher molecularweight dialkali metal polymeric hydrocarbon, although for conveniencethe same ether generally is selected. Other useful reaction mediainclude hexane, alkylate, benzene, triethylamine, and the like, andmixtures thereof.

The reaction of the higher molecular weight dialkali metal polymerichydrocarbon with the appropriate glycol-forming compound is generallycarried out at a temperature between about the reflux temperature of theselected reaction medium and about 60 C., or lower, and is preferablybetween about the reflux temperature and about -40 C. When no ether isused, however, the upper limit of operable temperatures can be higher,for example, as high as about C.

During the entire operation, that is, polymerization as well as glycolformation, it is important that the presence of moisture and compoundscontaining active hydrogen be carefully controlled in order to keep to aminimum the formation of monohydroxy compounds. It is also necessarythat other materials which would be reactive to the dialkali metaladduct be excluded. The reaction, therefore, should be conducted in aninert atmosphere to exclude moisture, oxygen, carbon dioxide, compoundscontaining active hydrogen, such as alcohols, esters, amines containingH on N, and the like, and other impurities. The reaction preferably iscarried out in an atmosphere of nitrogen or other inert gas, such ashelium or argon.

Although the process of this invention is applicable equally to anyglycol-forming reactant, for convenience it will be described withrelation to reaction with an epoxide; it is not, however, intended to belimited thereto.

The unsaturated glycol thus-formed is then halogenated. Although theprocess of this invention is applicable equally to any suitablechloride, bromide, or iodide reactant, for convenience it will bedescribed with relation to reaction with a chloride. It is not intended,however, to be limited thereto.

Halogenation products of the polymeric glycols may be produced by anyconvenient means, for example by the simple addition of chlorine to thedouble bonds of the glycol at a temperature between about 20 and 30 C.or by use of other halogenating agents such as sulfuryl chloride.

Although the use of a solvent is not essential, such solvents as carbontetrachloride, acetic acid, or carbon disulfide may be used. Preferredsolvents are those that are unreactive to the halogenating agent and arereadily removed from the halogenated glycol, such as for examplelow-boiling polychlorinated hydrocarbons.

The following general equations are presented to illustrate themechanism of the process of this invention, using butadiene, styrene,and ethylene oxide to represent the reactants:

(III) where (I) is a dialkali metal polymerized hydrocarbon; (II) is ahigh molecular weight glycol; (III) is the halogenated high molecularweight glycol product of this invention; a is a whole number of at least2, and preferably from 2 to about 200; b is or above; the ratio of b toa ranges from 0 to about 9 inclusive; X is a halogen atom; and n is awhole number ranging from about 2 to 2a, and preferably about to about200. The halogenation, as shown in Equation 3, occurs essentially withthe diolefinic segment of the main polymer chain.

Accordingly, the halogenated high molecular weight terminal glycols ofthis invention have the general formula wherein R is a divalenthydrocarbon radical, A is a diolefin radical, B is a radical selectedfrom the group consisting of styrene and alkyl-substituted styrenes, Xis a halogen, a is a whole number of at least 2, b is O to about 9a, mis 0 to 1, and n is a whole number ranging from about 2 to 2a. Themolecular weight of these compounds is at least 300, and generally is inthe range of about 300 to about 25,000.

Halogenation of the polymeric glycol introduces fireresistant propertiesto the resulting product. In addition, items fabricated from thehalogenated polymeric glycol, e.g., foams, coatings, and castings, haveimproved stiffness and chemical resistance. Chlorinated polybut adieneglycols are useful as coating materials when employed as the soleresinous composition or when employed with other film-formingcomponents, such as for example polyesters; alkyd resins; polyvinylchloride; vinyl chloridevinyl acetate copolymers; cellulose derivativessuch as cellulose acetate, ethyl cellulose, etc.; phenolic resins; andacrylic polymers. For example, chlorinated polybutadiene glycols may becombined with an alkyd resin in a simple blend or may be formulatedinto' the alkyd resin to supplement the polyhydric alcohols or toreplace partially some of the polyhydric alcohols, resulting in acoating composition having improved solvent resistance, fire resistance,and hardness.

Chlorinated products of a resinous glycol containing styrene-type units,e.g., ot-methylstyrene, vinyltoluene, and the like, in addition tobutadiene units exhibit improved compatability with the otherfi1m-forming component and, in some cases, improved hardness overcompositions based on the polybutadiene glycol.

The halogenated polymeric glycols of this invention also are useful forproducing castings, for example by dissolving the glycol in diisocyanatewith stirring and warming. Prior to the introduction of the isocyanate,it may, for convenience, be desirable to dissolve the glycol in asupplementary polyhydric compound, such as castor oil, poly(ethyleneadipate) having a molecular weight of about 2,000, or propylene glycolhaving a molecular weight of about 2,000.

Similarly, plastic sheets may be prepared from a halogenated resinousdiol, with or without supplementary diols, by reacting it with a dior apolyisocyanate; in such cases it is generally desirable to provideadequate opportunity for the polymerization reaction to reach completionat moderate temperatures, that is temperatures of about 70 to 100 C.

The more detailed practice of the invention is illustrated by thefollowing examples wherein parts are given by Weight unless otherwisespecified. These examples and embodiments are illustrative only, and theinvention is not intended to be limited thereto except as indicated bythe appended claims.

Example 1 To 1.71 parts of disodiooctadiene in a mixture of 50 parts ofdimethyl ether and 2.6 parts of alkylate was introduced 6.3 parts of1,3-butadiene at the rate of 15 pounds per hour while maintaining thetemperature at about 30 C. and agitating vigorously. Upon completion ofthe addition of the butadiene, the reaction mixture was stirred for anadditional 30 minutes at about 36 C. Two parts of ethylene oxide wasthen added, and stirring Was continued for 45 minutes at 30 C. Themixture was then ejected onto Dry Ice. The ether solvent was removed byevaporation, the residue was purged with steam, and the resultingaqueous emulsion was acidified with oxalic acid. The viscous product wasseparated from the aqueous layer, washed with water, dried under vacuumat to C. with concurrent removal of alkylate, and filtered. The finishedproduct had a hydroxyl number of 143.5 and an acid number of 0.6,indicating a diol having a molecular Weight of 779. Reaction with a 5percent excess of tolylene diisocyanate and an amine catalyst resultedin a rubbery solid, indicating the approximate functionality of theproduct to be 2.0.

Example 2 To 0.76 part of dilithiooctadiene in a mixture of 44 parts ofdimethyl ether and 1 part of a-lkylate was added 11 parts of1,3-butadiene at the rate of 94 pounds per hour. When the addition ofthe butadiene was complete, stirring was continued for 90 minutes at 30to -32 C. Then 2.5 parts of ethylene oxide was added, maintaining thetemperature at -30 C. The product, worked up as in Example 1, 'had aviscosity of 768 poises at 25 C., a hydroxyl number of 62.8, and an acidnumber of 0.4, corresponding to a diol having a molecular weight of1,780.

Example 3 To 1 part of cesium in 44 parts of dimethyl ether was added to9.8 parts of 1,3-butadiene at the rate of 12 parts per hour. When theaddition of the butadiene was com- 'plete, the mixture was stirred at-39 C. for 25 minutes. Then 1.5 parts of ethylene oxide was added over aperiod of 5 minutes at 39 C. After being stirred for an additional 10minutes, the reactor contents were removed and worked up as inExample 1. The viscous liquid product has an intrinsic viscosity of 0.26in xylene at 25 C., a hydroxyl nurrrber of 12.5, and an acid number of0.2, equivalent to a diol molecular weight of 8,850.

Example 4 In a manner similar to that described in Example 3,fifty-three parts of butadiene was reacted with 1 part of cesiumdispersed in dimethyl ether, and the polymer was terminated 'by reactionwith 1.5 parts of ethylene oxide. The product was isolated as a tacky,soft, milkywhite gum having a hydroxyl number of 2.0 and an apparentmolecular weight of 56,000. The gum could be cured via dicumyl peroxideor via tolylene diisocyanate to rubber stocks exhibiting attractivedegrees of elasticity and flexibility.

Example 5 To 7.1 parts of disodiopolybutadiene (from 0.6 part of sodiumand 6.5 parts of 1,3-butadiene) in 50 parts of dimethyl ether and 5parts of a'lkylate was added 2.5 .parts of styrene. The mixture wasstirred for 30 minutes at 30 C. Two parts of ethylene oxide was thenadded. After having been stirred for 34 minutes, the product was removedand worked up as in Example 1. The acidified and [dried product had ahydroxyl number of and an acid number of 0.5, corresponding to a diolhaving a molecular weight of 861.

Example 6 To 2.82 parts of disodiodiphenylbutane in 50 parts of dimethylether and parts of alkylate was added 6.5 parts of 1,3-butadiene over a68 minute period at an average temperature of 36 C. Ethylene oxide (2.0parts) was then added. After being stirred for 25 minutes, the productwas removed and worked up by the procedure described in Example 1. Theproduct had a hydroxyl number of 142.0 and an acid number of 0.8,corresponding to a diol having a molecular weight of 788.

Example 7 To 83.4 parts of disodiodiphenylbuta-ne (formed by a reactionof 81.5 parts of styrene with 19 parts of sodium) in a mixture of 975parts of dimethyl ether and 1000 parts of hexane was added 82.9 parts ofstyrene dissolved in an equal volume of a alkylate. The addition wascarried out at 38 C. with vigorous agitation. Ten minutes after thecompletion of addition of styrene, 40 parts of ethylene oxide was addedat 40 C., and agitation was continued for a period of 15 minutes. Theproduct was worked up as described in Example 1. There was obtained 183parts of an extremely viscous and nearly solid material having ahydroxyl number of 230, corresponding to a polystyrene glycol ofmolecular weight 488.

Example 8 To a reaction vessel equipped with a Dry-Ice cooled condenserterminated with a nitrogen purge, a low-temper-ature thermometer, agas-inlet tube, and an agitator were charged the following in the orderlisted: 3.0 parts of p-terphenyl, 1,950 parts of dimethyl ether, and 10parts of a fine dispersion of sodium in purified kerosene (2.3 parts ofsodium having a maximum particle size of about three microns).

Within minutes at 30 C. a blue color developed in the reaction mixture,indicating the formation of a sodioterphenyl complex. Then 5.4 parts of1,3-butadiene was added to yield disodiooctadiene (0.05 mole). After 30minutes 108 parts of 1,3 butadiene was introduced into the reactionmixture at the rate of 1.8 parts per minute while maintaining thetemperature at about -30 C. and agitating vigorously. Upon completion ofthe addition of the butadiene, the reaction mixture was stirred for anadditional 15 minutes at about -30 C. A 98 percent yield ofdisodiopolybutadiene was obtained. The product, unstable to air, wasreacted with water for purposes of identification. The resultinghydrocarbon oil was highly unsaturated (Hanus iodine number 405 andhydrogenation number 450 and had an intrinsic viscosity of 0.07 inxylene at 23 C.

When the butadiene addition was complete, 6.2 parts (0.14 mole) ofethylene oxide was added to 113 parts of the disodiopolybutadiene, atthe rate of 0.41 grams per minute, the reactor temperature beingmaintained at about 30 C. The reaction mixture was agitated vigorouslyfor an additional 10 minutes at about -30 C. and then poured onto DryIce. The ether solvent was removed from the reaction mixture byevaporation, and the residue was punged with steam and acidified. Theviscous, polymeric product which separated on top of the water layer wasdissolved in 440 parts (500 ml.) of henzene, and the organic solutionwas filtered and washed repeatedly with distilled water until theaqueous phase was neutral. The benzene and other volatile materials wereremoved from the organic solution by distillation at about 70 C. and apressure of 5 mm. of mercury. An 82% yield was obtained of alight-colored, slow-flowing, sticky resin having a viscosity ofapproximately 1,000 poises at room temperature and approximately 0.6poise Grams of iodine equivalent to the moles of hydrogen absorbed by100 grams of sample.

at a 50% concentration in ethylene acetate monoethyl ether. Thepolymeric glycol product had a hydroxyl number of 35, corresponding toan equivalent weight of 1,600 and a molecular weight of 3,200. Reactionwith a 5 percent excess of tolylene diisocyanate and an amine catalystresulted in a rubbery solid, indicating approximate difunctionality ofthe product.

Example 9 To a reaction vessel equipped with a Dry-Ice cooled condenserterminated with a nitrogen purge, a low-temperature thermometer, agas-inlet tube, and an agitator were charged the following in the orderlisted: 4.0 parts of naphthalene, 1,950 parts of dimethyl ether, and 2.5parts of a fine dispersion of lithium (0.75 part of metal) in mineraloil. At 35 C., parts of butadiene was added at the rate of 1.5 parts perminute. When the addition was complete, stirring was continued for 60minutes. Then 6.6 parts of ethylene oxide was added at a temperaturebetween about 35 and 25 C., and stirring was continued for 30 minutes.The mixture was then ejected onto Dry Ice. The ether solvent wasevaporated, the residue was purged with steam, and the resulting aqueousemulsion was acidified with oxalic acid. The viscous product was thenseparated from the aqueous layer, washed with water, dried under vacuumat to 125 C., and filtered. The product had a hydroxyl number of 72.4and an acid number of 0.1, corresponding to a diol having a molecularweight of 1,550. The viscosity of the product was 430 poises at 25 C.

Example 10 To a reaction vessel such as is described in Example 8 wereadded 3.0 parts of naphthalene, 1,950 parts of dimethyl ether, and 23.3parts of a fine dispersion of sodium (5.75 parts of metal) in purifiedkerosene. At 35 C., 115.5 parts of isoprene diluted with an equal volumeof purified hexane was added over a period of 69 minutes. The mixturewas stirred at 32 C. for 15 minutes after completion of the isopreneaddition. Then 22 parts of ethylene oxide was added over a 17-minuteperiod at an average temperature of 32 C. Stirring was continued for 10minutes, after which the reactor contents were removed and worked up asin Example 8. The acidified, dried product had a hydroxyl number of 82.7and acid number of 0.8, corresponding to a diol having a molecularweight of 1,350.

Example 11 To a reaction vessel equipped with a Dry-Ice cooled andnitrogen-purged condenser, a low-temperature thermometer, a gas-inlettube, and an agitator were charged the following materials in the orderlisted: 3.0 parts of naphthalene, 1,950 parts of dimethyl ether, 16.2parts of a fine dispersion of sodium (4.6 parts of metal) in thepurified kerosene, and 20.8 parts of styrene in an equal volume ofpurified kerosene. The mixture was stirred for 15 minutes at 33 C.Butadiene parts) was then added over a period of 43 minutes at anaverage temperature of 32 C. Then 17.6 parts of ethylene oxide wasadded. After being stirred for 10 minutes, the product was removed andworked up by the procedure described in Example 8. The acidified, driedproduct had a hydroxyl number of 63.6 and an acid number of 0.3,corresponding to a diol having a molecular weight of Example 12 Example8 was repeated, except that 24 parts of styrene oxide was used in placeof ethylene oxide. The acidified, dried product had a hydroxyl number of44.5 and an acid number of 0.5, corresponding to a diol having amolecular weight of 2,500.

Example 13 Fifty-two and four tenths parts of a resinous diol, preparedas embodied herein, was dissolved in 462.6 parts of carbontetrachloride; chlorine gas was bubbled through the stirred solution at15 to 20 C. for 2.8 hours. At the end of this time, 53.7 grams ofchlorine had been absorbed by the resinous diol. Evaporation of thesolvent yielded a light tan, solid product which was taken up in tolueneand washed with dilute sodium hydroxide and water. Removal of thetoluene yielded 34.5 parts of a light brown powder. A sample of thesolid product produced above was dissolved in acetone and cast as a 3-mil film on clean glass plate. The solvent was allowed to evaporate, andthe film was cured at 80 C.; a hard, resistant coating was obtained onthe glass. The film did not ignite readily when brought in contact witha flame, indicating fire-resistant properties.

Example 14 A resinous diol having a molecular weight of 1,200 andprepared as embodied herein, was chlorinated by the procedure of Example13 to a product having a molecular weight of 2,000. The chlorinatedproduct was dissolved in an equal weight of a resinous diol having amolecular weight of 2,000. To 30 parts of the resulting mixture wereadded 0.86 part of water, 0.50 part of a silicone resin (Union CarbideCorporations L-520), 0.12 part of triethylene diamine, 0.39 part ofN-ethylmorpholine, and 0.05 part of stannous octoate. The resultingcomposition was agitated with a high-speed mixer for 5 to seconds, 1.28parts of tolylene diisocyanate was introduced quickly, and the mixturewas agitated for an additional 5 to 10 seconds. The resulting foamingmixture was poured into a mold and allowed to rise to full height. Curewas complete-d by placing the foam in an oven at 100 C. for one to twohours. The product foam was semi-rigid and exhibited fire-resistantproperties that were superior to those of normal polyurethan foams. Thesemi-rigid, fire-resistant foam was suitable for use in specializedpackaging for shipments where fire code requirements call for theseproperties.

While there are above disclosed but a limited number of embodiments ofthe invention herein presented, it is possible to produce still otherembodiments without departing from the inventive concept hereindisclosed. It is desired, therefore, that only such limitations beimposed on the appended claim as are stated therein.

What is claimed is:

A halogenated terminal glycol having a molecular weight in the range ofabout 300 to about 25,000 and having the general formula wherein A is apolymerized diolefin unit selected from the group consisting ofbutadiene and isoprene, B is a unit of polymerized monomer selected fromthe group consisting of styrene and alkyl-substituted styrenes, a is awhole number ranging from 2 to about 200, b is 0 to about 1800, theratio of b to a ranges from 0 to about 9 inclusive, in ranges from 0 to1 inclusive, and n is a whole number ranging from about 2 to 2a; saidhalogenated terminal glycol being that which is obtained by halogenatinga compound having the general formula wherein A, B, a, b and m are asdefined above, with a halogenating agent selected from the groupconsisting of elemental chlorine and sulfuryl chloride at a temperaturebetween about and C.

References Cited by the Examiner UNITED STATES PATENTS 2,773,092 12/1956Carly et a1. 260-635 X 2,850,538 9/1958 Nobis et a1. 260635 2,985,5945/1961 Zimmermann 260-618 3,055,952 9/1962 Goldberg 2606l8 3,175,9973/1965 Hsieh 260-635 OTHER REFERENCES Wagner et al.: Synthetic OrganicChemistry, N.Y., J. Wiley & Sons, Inc., 1953, pp. 106-107.

LEON ZITVER, Primary Examiner.

CHARLES B. PARKER, Examiner.

A. H. SUTTO, M. B. ROBERTO, J. M. BANE, T. G.

DILLAHUNTY, Assistant Examiners.

